Synthesis and use of grafted graphene in oil based drilling fluids as low shear rate viscosity enhancer

ABSTRACT

A composition that includes a polymer-grafted graphene particle and oil-based drilling fluid is provided. At least one side of the graphene particle comprises a grafted polymer. A method of using an oil-based drilling fluid is also provided. The method includes introducing the oil-based drilling fluid into a wellbore and circulating the oil-based drilling fluid during drilling operations. The drilling fluid includes a polymer-grafted graphene particle and oil-based drilling fluid. At least one side of the graphene particle comprises a grafted polymer. The oil-based drilling fluid includes a range of from about 0.01 ppb to 10 ppb of the polymer-grafted graphene particle.

BACKGROUND

During drilling operations, a drilling fluid, which may also be referred to as drilling mud, is circulated through the wellbore to cool and lubricate the drill bit, to convey rock cuttings to the surface, and to support the wellbore against collapse and intrusion of fluids from the formation, among other purposes. Drilling fluids are formulated to have certain fluid characteristics, such as density and rheology, for example, that allow the drilling fluid to perform these functions. When circulation stops, the drill cuttings must remain suspended in the fluid. Under certain extreme downhole conditions, such as excessive temperature, for example, some of the properties of the drilling fluid may be altered.

SUMMARY

This summary is provided to introduce a selection of concepts that are further described in the detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.

In one aspect embodiments disclosed herein relate to a composition that includes a polymer-grafted graphene particle and oil-based drilling fluid. At least one side of the graphene particle comprises a grafted polymer.

In another aspect, embodiments disclosed herein relate to a method of using an oil-based drilling fluid. The method includes introducing the oil-based drilling fluid into a wellbore and circulating the oil-based drilling fluid during drilling operations. The drilling fluid includes a polymer-grafted graphene particle and oil-based drilling fluid. At least one side of the graphene particle comprises a grafted polymer. The oil-based drilling fluid includes a range of from about 0.01 ppb to 10 ppb of the polymer-grafted graphene particle.

Other aspects and advantages of the claimed subject matter will be apparent from the following description and the appended claims.

DETAILED DESCRIPTION

Rheological properties of drilling fluids are important for safely and effectively drilling a well. Drilling fluid must be capable of maintaining good rheological properties under extreme environments, such as elevated temperature and pressure. An important rheological property of drilling fluid is yield point. A high yield point implies a non-Newtonian fluid. Fluids with higher yield points are better able to carry drill cuttings to the surface and keep formation cuttings suspended in the drilling fluid when circulation is paused. The present disclosure relates to a drilling fluid composition including a polymer grafted graphene particle. Disclosed compositions may provide increased yield point as compared to compositions that do not include polymer grafted graphene particles.

Polymer Grafted Graphene Particle

One or more embodiments include polymer-grafted graphene particles that include graphene. The graphene used to form the one or more embodiment particles may have a hexagonal crystal structure. Graphene typically has a bulk density of from about 0.03 to about 1.0 g/cm² (grams per centimeter squared).

Graphene used for one or more embodiments may be an appropriate size for use as part of an oil-based drilling fluid or “mud”. For example, the graphene may have a thickness in a range of from about 0.5 to 20 nm (nanometers), a length in a range of from about 0.5 to 50 μm (micrometers), and a width in a range of from about 0.5 to 50 μm; however, this may vary according to the needs of the application.

Graphene used for one or more embodiments may be an appropriate shape for use in an oil-based drilling fluid. For example, graphene particles may be flat or non-flat sheets that are in common geometric shapes, such as circular, square, and triangular forms. Geometric and non-geometric configurations are not limited except as to provide for a surface for grafting with a polymer.

Graphene used for embodiment particles may have appropriate surface chemistry for use as in oil-based muds. In some embodiments, the graphene surface is hydrophobic, meaning the graphene surface has a water contact angle of greater than 90°.

Embodiment polymer-grafted graphene particles also include a polymer that is grafted to at least one side of the graphene particle. In embodiments in which a polymer is grafted to one side of the graphene particle and the other side of the graphene particle does not include a polymer, the particle may be referred to as a “mono-facial polymer grafted graphene particle”. In such embodiments, graphene particles have a “Janus-like” structure due to the difference in functionality of the polymer-grafted side and the graphene side. In embodiments in which both sides of the graphene particle are grafted with a polymer (i.e., a first side and a second side), the particle may be referred to as a “bi-facial polymer grafted graphene particle”.

The grafted polymers may be made from any suitable monomer that is configured to graft to a graphene particle and provide sufficient hydrophobicity for use in oil-based drilling fluid. The polymer may be formed by grafting a monomer unit to a graphene oxide surface and polymerizing one or more types of monomers together to form a polymer. A monomer reacts with the surface of graphene oxide to form a grafted monomer unit. Additional monomer units then add to the grafted monomer unit to form a grafted polymer. The length of the polymer may be formed from a polymerization reaction of from about 5 monomer units to about 200 monomer units. The polymers may be formed using hydrophobic monomers, hydrophilic monomers, and combinations thereof, so they are suitable for use in oil-based muds. Polymers may include any suitable molecular structure, such as linear, branched, random, alternating, block, and grafted.

Monomers in accordance with the present disclosure may be compatible with oil-based muds. In one or more embodiments, monomers having a hydrocarbon chain may have a hydrocarbon chain with at least 5 carbons atoms. Suitable monomers may include but are not limited to 2-acrylamido-2-methylpropane sulfonic acid (AMPS), N,N-dimethylacrylamide (NNDMA), acrylic acid amide (AM), acrylic acid (AA), itaconic acid (IA), maleic anhydride (MA), lauryl acrylate (LA), stearyl acrylate (SA) and combinations thereof. Polymers may be formed from a single type of monomer or from multiple monomer types. In one embodiment, the polymer may include units of a single monomer type. In another embodiment, the polymer may include units of a first monomer type and second monomer type. In yet another embodiment, the polymer may include units of a first monomer type, second monomer type, and a third monomer type.

In embodiments in which two different monomers are used (also referred to as a copolymer), the copolymer may include from 30-70 mol % of units derived from a first monomer and from 30 to 70% of units derived from a second monomer. In particular embodiments, the copolymer may include about 50 mol % of units derived from the first monomer and 50 mol % of units derived from the second monomer.

In embodiments in which three different monomers are used (also referred to as a terpolymer), the terpolymer may include from 30 to 60 mol % of units derived from a first monomer, from 30 to 60 mol % of units derived from a second monomer and 1 to 10 mol % of units derived from a third monomer. In particular embodiments, the terpolymer may include about 45 mol % of units derived from the first monomer, about 45 mol % of units derived from the second monomer, and about 10 mol % of units derived from the third monomer.

A combination of different monomers may be used in order to provide certain properties. For example, some monomers, such as AMPS, provide salinity tolerance. Other monomers, such as lauryl acrylate, provide hydrophobicity. Thus, using a combination of AMPS and lauryl acrylate may provide an oil-soluble polymer with high salinity tolerance. Generally, monomers disclosed herein result in a hydrophobic polymer that is suitable for use in oil-base muds.

In a non-limiting exemplary embodiment, the polymer may be a copolymer including units derived from AA monomers and units derived from AMPS monomers. In another non-limiting exemplary embodiment, the polymer may be a copolymer including units derived from AMPS monomers and units derived from LA monomers. In embodiments in which a terpolymer is used, any of the previously described comonomers may further include IA monomers, which may improve thermal stability. An additional non-limiting embodiment of a terpolymer may be a terpolymer with units derived from AMPS, LA and NNDMA. Finally, a polymer having units derived from AMPS, NNDMA, IA and LA may also be suitable in one or more embodiments.

Method of Making Mono-Facial Polymer Grafted Graphene Particle

One or more embodiments relate to a method of making a mono-facial polymer-grafted graphene particle. One or more embodiments may include preparing an emulsion, adding one or more monomers to the emulsion, initiating polymerization, and polymerizing the monomer(s) to form the embodiment mono-facial polymer-grafted graphene particle.

Embodiment methods may include preparing an emulsion. The preparing step may include mixing water, wax, and graphene oxide, at an elevated temperature, and agitating the mixture to form an emulsion. The term “elevated temperature” means a temperature that is greater than room temperature. The elevated temperature for preparing the emulsion is not particularly limited provided that the elevated temperature is in a range that is greater than the melting temperature of the wax and is less than the boiling point of water. In some embodiments, the temperature is in a range of from about 60 to 90° C.

In preparing the emulsions, appropriate amounts of water and graphene oxide are mixed and agitated, creating a slurry. Such agitation may include stirring, sonication, and other suitable agitation methods, to distribute the graphene oxide particles homogenously throughout the water. Then, wax may be added to the graphene/water slurry to create a second slurry—a wax-in-water slurry. The wax may be added gradually as a solid. In one or more embodiments, as the solid wax particles heats, the molten wax droplets form. In such instances, the molten wax droplets may have a diameter of from about 0.05 to 100 μm (micrometers or microns). The second slurry may be agitated to form an emulsion of wax in water with graphene oxide particles.

The emulsions may comprise water in a range of from about 50 to 85 wt % (weight percent), graphene oxide in a range of from about 10 to 30 wt %, and wax in a range of from about 10 to 35 wt %. The amounts of water, graphene oxide, and wax may be adjusted to achieve a desired droplet size of the molten wax in the slurry.

In one or more embodiments, an acid, such as hydrochloric acid, may be present in an amount in a range of from about 0.03 to 0.1 wt % of the emulsion as compared to the mass of water. The HCl is used to adjust the pH of the emulsion to a range of about 2 to 3.

During the emulsification of the second slurry, graphene oxide collects at the interface of the water and the molten wax, forming a Pickering emulsion. The graphene oxide has wax affiliated with one of its two opposing surfaces; water with the other. Once the Pickering emulsion has formed, the emulsion may then be cooled such that the wax droplets re-solidify. Upon solidification, the wax particles (formerly droplets) are coated in the graphene oxide particles; the graphene particles are attached to the surface of the wax. The wax particles coated with graphene oxide particles may be separated from the water using known means in the art, such as by filtration.

The wax/graphene oxide particles may be dispersed in a solution of sodium hydroxide at a pH of about 10, agitated for about 5 to 10 minutes, filtered, and recovered.

Embodiment methods include forming a suspension with the previously separated wax/graphene oxide particles. The wax/graphene oxide particles may be suspended in a solution of equal parts water and ethanol by weight. Into the suspension an amount of monomer and initiator is added. The weight ratio of graphene:monomer may be in a range of from about 1:1 to about 1:20. Suitable initiators may include, but are not limited to, α-bromoisobutyryl bromide (referred to here as “ATRP”) and trithiocarbonates (referred to here as “RAFT agents”). The initiator may be included in an amount ranging from about 2 to 15 mol % (mole percent) based on the amount of monomer(s). In embodiments in which a copolymer is being synthesized, about a 1:1 molar ratio of monomers may be used. In embodiments in which a terpolymer is being synthesized, about a 4.5:4.5:1 molar ratio of a first, second and third monomer may be used.

Once a monomer(s) and initiator are added, the suspension is stirred for a period in a range of from about 5 to 24 hours at a temperature of in a range of from about 30 to 90° C. to facilitate polymerization on the non-wax side of the graphene particle. Polymerization generally does not occur at a temperature that would melt the wax particles. The rate of polymerization may be increased by utilizing increased reaction temperatures. The reaction time typically does not control the length of the polymer chains. The length of the polymer chains is determined by the amount of monomer(s) added to the suspension.

Once polymerization is complete, mono-facial polymer grafted graphene particles have formed. In order to recover the embodiment mono-facial polymer grafted graphene particles from the surface of the wax particles, the wax particles are heated to a temperature greater than the melting point of the wax, generally in a range of from about 60 to about 95° C. The embodiment mono-facial polymer-grafted graphene particle is separated via filtration. The embodiment particles may be rinsed with warm water to remove residual wax from the non-polymerized side of the particle. The embodiment mono-facial polymer grafted graphene particles may be stored as a powder.

Method of Making Bi-Facial Polymer Grafted Graphene Particle

One or more embodiments relate to a method of making a bi-facial polymer-grafted graphene particle. One or more embodiments may include preparing dispersion of graphene oxide, adding one or more monomers to the dispersion, initiating polymerization, and polymerizing the monomer(s) to form the embodiment bi-facial polymer-grafted graphene particle.

Embodiment methods may include preparing a dispersion of graphene oxide in a solvent. The preparing step may include adding an appropriate amount of solid graphene oxide to a solvent such as dimethylformamide (DMF) to create a dispersion. The dispersion may then be agitated, such as by sonication, to exfoliate the graphene oxide into individual sheets. After agitating the dispersion, aggregated graphene oxide is removed by centrifugation while exfoliated graphene oxide remain dispersed in the DMF.

Polymerization of the graphene oxide is conducted in a manner similar to the previously described process for mono-facial graphene particles. An amount of monomer and initiator is added to the dispersion of graphene oxide in DMF. The weight ratio of graphene:monomer(s) may be in a range of from about 1:1 to about 1:20. Suitable initiators may include, but are not limited to, α-bromoisobutyryl bromide (referred to here as “ATRP”) and trithiocarbonates (referred to here as “RAFT agents”). The initiator may be included in an amount ranging from about 2 to 15 mol % (mole percent) based on the amount of monomer(s). If co- or terpolymers are being made, ratios of each of the monomers may be as previously described.

Once a monomer(s) and initiator are added, the dispersion is stirred for a period in a range of from about 5 to 24 hours at a temperature of in a range of from about 30 to 90° C. to facilitate polymerization. The rate of polymerization may be increased by utilizing increased reaction temperatures. The reaction time typically does not control the length of the polymer chains. The length of the polymer chains is determined by the amount of monomer(s) added to the suspension.

Once polymerization is complete, bi-facial polymer grafted graphene particles have formed. The particles may be filtered from the solvent and stored as a powder.

In an exemplary embodiment, about 2.5 g of graphene oxide may be dispersed in about 1 L of DMF by ultrasonication for 2 hours in an ice batch to avoid heat generation. The dispersed suspension may be transferred to a 2 L round bottom flask equipped with magnetic stirring. Then 10 mL of trimethylamine (TEA) may be added and the solution stirred for 10 minutes. 40 mL of ATRP may be diluted with DMF and added dropwise to the GO suspension in ice bath. After stirring in ice bath for 1 hour, the reaction may be allowed to age at room temperature for 3 days. The resulted product may be purified by centrifugation at 4.4 krpm for 10 min to remove the DMF. The precipitate may be washed three times with reagent alcohol for 3 times with centrifugation. Then the final product may be dried under vacuum at 50° C. to remove solvent for 2 days.

An Oil-Based Drilling Fluid with Polymer Grafted Graphene Particle

In another aspect, embodiments disclosed relate to a composition of matter of an oil-based drilling fluid with the previously described polymer-grafted graphene particle.

One or more embodiments of the drilling fluid include an oil-based fluid. The oil-based drilling fluid may also be referred to as an invert emulsion. The oil-based fluid includes an oil. The oil may be crude oil, refined oils, such as diesel and mineral oils, non-petroleum organics, and combinations thereof, that are suitable for use in a wellbore environment. In one or more embodiments, the oil used may naturally contain contaminants, such as salts, minerals, and combinations thereof, as long as the contaminants do not interfere with the operation of the drilling fluid.

In one or more embodiments, the drilling fluid may contain oil in a range of from about 50 wt % to 97 wt % based on the total weight of the drilling fluid. In one or more embodiments, the embodiment drilling fluid may comprise greater than 70 wt % water based on the total weight of the drilling fluid.

An invert emulsion oil-based drilling fluid includes an inverted phase, called an aqueous phase. The aqueous phase may contain water. The water may be distilled water, deionized water, tap water, fresh water from surface or subsurface sources, production water, formation water, natural and synthetic brines, brackish water, natural and synthetic sea water, black water, brown water, gray water, blue water, potable water, non-potable water, other waters, and combinations thereof. In one or more embodiments, the water may be deionized water. In other embodiments, the water may be a brine. In still other embodiments, the water may be a mixture of deionized water and a brine. In one or more embodiments, the aqueous phase is a brine, such as a calcium chloride anhydride-based brine. The brine may be in a range of 5 to 40 vol % compared to the total volume of the drilling fluid formulation.

In one or more embodiments, the drilling fluid may comprise an aqueous phase in an amount that ranges from about 5 to 40 vol % (volume percent) based on the total volume of the drilling fluid. For example, the drilling fluid may contain an aqueous phase in an amount ranging from a lower limit of any of 5, 7, 10, 12, 15, and 20 vol %, to an upper limit of any of 25, 30, 35 and 40 vol % based on the total volume of the drilling fluid, where any lower limit can be used in combination with any mathematically-compatible upper limit.

One or more embodiments of the drilling fluid include an emulsifier. Including an emulsifier in an oil-based mud lowers the interfacial tension between oil and water, providing a stable emulsion. The drilling mud may include commercially available emulsifiers such as VersaMul® supplied by MI Swaco, EnduraMul®, EZMUL® supplied by Halliburton, and combinations thereof.

Embodiment drilling fluid may comprise one or more emulsifiers in an amount ranging from about 5 to about 15 ppb. For example, the drilling fluid may contain one or more emulsifiers having a lower limit of one of 5, 6, 7, 8 and 9 and an upper limit of one of 10, 11, 12, 13, 14 and 15, where any lower limit may be paired with any mathematically compatible upper limit.\

In one or more embodiments, the drilling fluid may comprise a wetting agent. In drilling mud, wetting agents are surfactants often used to reduce the sticking tendencies of clay and shale. Drilling mud in accordance with the present disclosure may include commercially available wetting agents such as VersaCoat®, supplied by Mi Swaco and EZMUL® suppled by Halliburton.

In one or more embodiments, the drilling fluid may comprise a wetting agent in an amount ranging from about 1 to about 10 ppb. For example, the wetting agent may be present in an amount having a lower limit of one of 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, and 5 ppb and an upper limit of one of 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, and 10 ppb, where any lower limit may be paired with any mathematically compatible upper limit.

A weighting agent refers to finely divided solid material that is used to increase the density of the invert emulsion oil-based drilling fluid formulation. Non-limiting examples of weighting agents include aragonite, bentonite, barite, barium chloride, barium hydroxide, barium oxide, barium sulfate, calcite, calcium carbonate, dolomite, hematite, ilmenite, iron carbonate, iron oxides, lead carbonate, manganese oxides, siderite, zinc carbonate, zinc oxide, zirconium oxide, and other various minerals. In one or more embodiments, the additive includes barite or manganese tetroxide as a weighting agent.

In one or more embodiments, the weighting agent is provided in a concentration range of from 0.5 to 300 parts per billion (ppb) in the overall composition.

In one or more embodiments, the drilling fluid may comprise a suitable amount of the previously described polymer-grafted graphene particle to increase yield point and low shear yield point of the drilling fluid. In one or more embodiments, the polymer-grafted graphene particle is present in embodiment drilling fluid in a range of from about 0.01 ppb to 10 ppb. For example, the drilling fluid may contain the polymer-grafted graphene particle in an amount ranging from a lower limit of any of 0.01, 0.05, 0.10, 0.25, 0.5, 1.0, 1.5 and 2.0 ppb, to an upper limit of any of 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0, 7.0, 8.0, 9.0, and 10.0 ppb, where any lower limit can be used in combination with any mathematically-compatible upper limit.

In one or more embodiments, the drilling fluid may have a density in a range of from about 8 to 22 ppg (pounds per gallon).

Embodiment drilling fluids comprising the polymer-grafted graphene particle may have improved properties as compared to drilling fluids without the polymer-grafted graphene particle. Such improvements may include an increased yield point (YP) and low shear yield point (LSYP) across a range of temperatures and pressures.

In one or more embodiments, drilling fluids comprising the polymer-grafted graphene particle may have an improvement in low shear yield point of at least 25%, at least 50%, at least 75%, at least 100%, at least 125%, at least 150%, at least 175% or at least 200% as compared to a control drilling fluid that does not have graphene.

While the present disclosure describes using polymer-grafted graphene particles in drilling fluids, the disclosed particles may be used in a variety of fluids in oil and gas applications. As may be appreciated by those skilled in the art, embodiment polymer-grafted graphene particles may be useful in completion fluids, workover fluids, spacer fluids, cement compositions and others.

Method of Using an Aqueous-Based Drilling Fluid with Polymer Grafted Graphene Particle

One or more embodiments of the present disclosure related to using the previously described oil-based drilling fluid having a polymer grafted graphene particle in a hydrocarbon bearing formation. Embodiment methods include introducing the previously described oil-based drilling fluid into a wellbore and then circulating the oil-based drilling fluid in the wellbore during drilling operations.

Examples

All materials had a purity of 99% or greater and were used as received unless otherwise indicated.

Preparation of Bi-Facial Polymer-Grafted Graphene in Mud A

GO-ATRP (5 g) was dispersed in DMF (1 L) by ultrasonication for 2-3 hours with ice bath cooling to make sure it dispersed well in DMF. AMPS monomer (100 g) was dissolve in 200 mL water. The solution was neutralized with a sufficient amount of sodium hydroxide until the pH is higher than 7. Then the water solution was mixed with the DMF suspension and 1.5 g of copper(I) bromide was added to the mixed solution. A 1:1 molar ratio of LA was added to the solution and transferred to a 2 L round bottom flask equipped with septum and magnetic stirrer. Then the solution was purged with nitrogen for one hour to remove oxygen in the system. 12 mL PMTEMA was added by syringe and the flask was placed in an oil bath preheated to 80° C. The reaction was allowed to proceed for 2-3 days. The raw product was centrifuged at 4.4 krpm for 10 minutes to remove the supernatant, and then washed with reagent alcohol at least 3 times until no color was visible in the supernatant. Then the sediment GO-AMPS-r-LA was dried under vacuum at 50° C. for 2 days (the “r” indicates a random polymer).

Preparation of Bi-Facial Polymer Grafted Graphene for Mud C

GO-ATRP (5 g) was dispersed in DMF (1 L) by ultrasonication for 2-3 hours with ice bath cooling to make sure it dispersed well in DMF. AMPS monomer (100 g) was dissolve in 200 mL water. The solution was neutralized with a sufficient amount of sodium hydroxide until the pH is higher than 7. Then the water solution was mixed with the DMF suspension and 1.5 g of copper(I) bromide was added to the mixed solution. Then the solution was purged with nitrogen for one hour to remove oxygen in the system. It was transferred to a 2 L round bottom flask equipped with septum and magnetic stirrer. 12 mL PMTEMA was added by syringe and the flask was placed in an oil bath preheated to 80° C. The reaction was allowed to proceed for 1-2 days. A 1:1 molar ratio of LA was added. The reaction was allowed to proceed for 2-3 days. The raw product was centrifuged at 4.4 krpm for 10 minutes to remove the supernatant, and then washed with reagent alcohol at least 3 times until no color was visible in the supernatant. Then the sediment GO-AMPS-b-LA was dried under vacuum at 50° C. for 2 days (the “b” indicates a block copolymer).

The resultant products of Muds A and C were used to prepare mud samples #2 and #4 in Table 1, respectively.

Mud Preparation

Graphene used in the mud samples was GO-V50 obtained from Standard Graphene.

Oil-based mud samples were prepared in a Hamilton beach multi-mixer. Unless otherwise specified, a mixing speed of 12000 rpm (revolutions per minute) was used. Each sample was prepared by starting with diesel and then adding each of the components listed in Table 1, followed by the amount of stirring time indicated for that component in Table 1.

The oil-based mud samples including the mass (grams) of each mud component is shown in Table 1. Sample #1 is a mud sample having no graphene additive. Thus, sample 1 serves as a comparative example. Sample 3 includes graphene with no polymer modifications. Samples 2 and 4 are inventive compositions.

TABLE 1 Weight (ppb) and mud type Additive Type Control Mud A Mud B Mud C Sample Number Mixing time #1 #2 #3 #4 Diesel 178.3 178.3 178.3 178.3 Graphene Sonicate, 0 1 1 1 Additive 2 hours Viscosifier 2 min, 2 2 2 2 12000 RPM Emulsifier 2 min, 5-10 5-10 5-10 5-10 12000 RPM Wetting Agent 2 min, 2 2 2 2 12000 RPM Lime 2 min, 10 10 10 10 12000 RPM Rheological 2 min, 3 3 3 3 Modifier 12000 RPM Shear 20 minutes at 12000 RPM CaCl₂ brine in 2 min, 71.85 71.85 71.85 71.85 DI water 12000 RPM Fluid loss 2 min, 2 2 2 2 additive 12000 RPM Barite 2 min, 280 280 280 280 12000 RPM Drill Solid 2 min, 50 50 50 50 12000 RPM Shear 20 minutes at 12000 RPM

After mixing, all muds were hot-rolled at 300° F. under 500 psi of nitrogen pressure for 16 hours. Then the samples were tested at 150° F. with Fann 35 Rheometer in accordance with the American Petroleum Institute (API) Bulletin 13D. The results of the rheology testing are shown in Table 2, below.

TABLE 2 RPM Sample 1 Sample 2 Sample 3 Sample 4 600 69 76 72 86 300 43 50 45 54 200 32 39 35 42 100 21 27 24 29  6 6 15 7 14  3 5 14 6 13 10 s 9 16 9 19 10 min 18 20 19 21 PV (cP) 26 26 27 32 YP (lb/100 ft²) 17 24 18 22 LSYP (lb/100 ft²) 4 13 5 12 % improvement in YP N/A 41% 5.88% 29.4% over control

As shown in Table 2, samples 2 and 4 had higher yield points and higher low shear yield point values as compared to the control sample 1 that included no graphene additive. Samples 2 and 4 also had higher yield point and low shear yield point than sample 3, which included graphene that had not been grafted with a polymer.

The singular forms “a,” “an,” and “the” include plural referents, unless the context clearly dictates otherwise.

As used here and in the appended claims, the words “comprise,” “has,” and “include” and all grammatical variations thereof are each intended to have an open, non-limiting meaning that does not exclude additional elements or steps.

When the word “approximately” or “about” are used, this term may mean that there can be a variance in value of up to ±10%, of up to 5%, of up to 2%, of up to 1%, of up to 0.5%, of up to 0.1%, or up to 0.01%.

Ranges may be expressed as from about one particular value to about another particular value, inclusive. When such a range is expressed, it is to be understood that another embodiment is from the one particular value to the other particular value, along with all particular values and combinations thereof within the range.

While the disclosure includes a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments may be devised which do not depart from the scope of the present disclosure. Accordingly, the scope should be limited only by the attached claims.

Thus, particular implementations of the subject matter have been described. Other implementations are within the scope of the following claims

Although only a few example embodiments have been described in detail, those skilled in the art will readily appreciate that many modifications are possible in the example embodiments without materially departing from the scope of the disclosure. Accordingly, all such modifications are intended to be included within the scope of this disclosure as defined in the following claims. In the claims, means-plus-function clauses are intended to cover the structures described as performing the recited function and not only structural equivalents, but also equivalent structures. Thus, although a nail and a screw may not be structural equivalents in that a nail employs a cylindrical surface to secure wooden parts together, whereas a screw employs a helical surface, in the environment of fastening wooden parts, a nail and a screw may be equivalent structures. It is the express intention of the applicant not to invoke 35 U.S.C. § 112(f) for any limitations of any of the claims, except for those in which the claim expressly uses the words ‘means for’ together with an associated function. 

What is claimed:
 1. A composition of matter comprising: a polymer-grafted graphene particle, wherein at least one side of the graphene particle comprises a grafted polymer; and oil-based drilling fluid.
 2. The composition of claim 1, wherein the grafted polymer is polymerized from a monomer selected from the group consisting of 2-acrylamido-2-methylpropane sulfonic acid, N,N-dimethylacrylamide, acrylic acid amide, acrylic acid, itaconic acid, maleic anhydride, lauryl acrylate, stearyl acrylate and combinations thereof.
 3. The composition of claim 1, wherein a first side of the graphene particle comprises the grafted polymer and a second side does not.
 4. The composition of claim 1, wherein a first side and a second side of the graphene particle comprise the grafted polymer.
 5. The composition of claim 1, wherein the polymer is comprised of units of a single monomer type.
 6. The composition of claim 1, wherein the polymer is comprised of units of a first monomer type and a second monomer type.
 7. The composition of claim 1, wherein the polymer is comprised of units of a first monomer type, a second monomer type and a third monomer type.
 8. The composition of claim 1, comprising a range of from about 0.01 ppb to 10 ppb of the polymer-grafted graphene particle.
 9. The composition of claim 1, comprising an improvement in yield point of at least 40% as compared to a control that does not include the polymer-grafted graphene particle.
 10. The composition of claim 1, comprising an improvement in low shear yield point of at least 100% as compared to a control that does not include the polymer-grafted graphene particle.
 11. A method of using an oil-based drilling fluid, the method comprising: introducing the oil-based drilling fluid into a wellbore, the drilling fluid comprising a polymer-grafted graphene particle; and circulating the oil-based drilling fluid during drilling operations; wherein at least one side of the graphene particle comprises a grafted polymer; and wherein the oil-based drilling fluid comprises a range of from about 0.01 ppb to 10 ppb of the polymer-grafted graphene particle.
 12. The method of claim 11, wherein the grafted polymer is polymerized from a monomer selected from the group consisting of 2-acrylamido-2-methylpropane sulfonic acid, N,N-dimethylacrylamide, acrylic acid amide, acrylic acid, itaconic acid, maleic anhydride, lauryl acrylate, stearyl acrylate and combinations thereof.
 13. The method of claim 11, wherein a first side of the graphene particle comprises the grafted polymer and a second side does not.
 14. The method of claim 11, wherein a first side and a second side of the graphene particle comprise the grafted polymer.
 15. The method of claim 11, wherein the polymer is comprised of units of a single monomer type.
 16. The method of claim 11, wherein the polymer is comprised of units of a first monomer type and a second monomer type.
 17. The method of claim 11, wherein the polymer is comprised of units of a first monomer type, a second monomer type and a third monomer type.
 18. The method of claim 11, wherein the oil-base drilling fluid comprises a range of from about 0.01 ppb to 10 ppb of the polymer-grafted graphene particle.
 19. The method of claim 11, wherein the oil-base drilling fluid comprises an improvement in yield point of at least 40% as compared to a control that does not include the polymer-grafted graphene particle.
 20. The method of claim 11, wherein the oil-base drilling fluid comprises an improvement in low shear yield point of at least 100% as compared to a control that does not include the polymer-grafted graphene particle. 